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EP0360038B1 - Procédé de préparation de copolymères amine modifiés de l'éthylène et d'acides carboxyliques, ces copolymères et leur application aux produits adhésifs et aux matériaux d'isolation de cables - Google Patents

Procédé de préparation de copolymères amine modifiés de l'éthylène et d'acides carboxyliques, ces copolymères et leur application aux produits adhésifs et aux matériaux d'isolation de cables Download PDF

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Publication number
EP0360038B1
EP0360038B1 EP89115873A EP89115873A EP0360038B1 EP 0360038 B1 EP0360038 B1 EP 0360038B1 EP 89115873 A EP89115873 A EP 89115873A EP 89115873 A EP89115873 A EP 89115873A EP 0360038 B1 EP0360038 B1 EP 0360038B1
Authority
EP
European Patent Office
Prior art keywords
ethylene
copolymers
amine
copolymerization
carboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89115873A
Other languages
German (de)
English (en)
Other versions
EP0360038A2 (fr
EP0360038A3 (fr
Inventor
Norbert Dr. Hasenbein
Thomas Dr. Mühlenbernd
Gernot Dr. Koehler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT89115873T priority Critical patent/ATE101624T1/de
Publication of EP0360038A2 publication Critical patent/EP0360038A2/fr
Publication of EP0360038A3 publication Critical patent/EP0360038A3/fr
Application granted granted Critical
Publication of EP0360038B1 publication Critical patent/EP0360038B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the invention relates to a process for the production of high molecular weight ethylene copolymers with melt indices of less than 40 g / 10 min by copolymerization of ethylene with ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, carboxylic anhydrides and / or their derivatives in a polymerization system at pressures of 500 to 5000 bar and Temperatures of 40 to 350 ° C in the presence of free radical decomposition polymerization initiators and optionally molecular weight regulators.
  • Such processes produce high molecular weight, carboxyl group-containing ethylene copolymers which can be used as adhesion promoters or in cable jackets or, after neutralization with inorganic or organic salts, can be converted into ionomers.
  • the task was to find a process for the production of amine-modified high molecular weight ethylene copolymers, in which the production takes place in one step and in which the products have increased homogeneity, excellent gloss, good transparency and puncture resistance of the films.
  • the tertiary organic amine is preferably copolymerized in the presence of 10 to 100, in particular 30 to 95 mol%, based on the unsaturated carboxylic acid compound used.
  • the object was further achieved by high molecular weight ethylene copolymers which had been modified by the above process using monovalent tertiary amines.
  • the copolymerization can be carried out in any high pressure polymerization reactor. Autoclaves, autoclave-tube reactor combinations and in particular also simple single-zone tube reactors are possible. This is surprising since the manufacture is reasonably homogeneous ethylene copolymers without prior amine modification, especially at high comonomer concentrations, can otherwise only be carried out in an autoclave.
  • tubular reactor to be used preferably according to the invention is a single-zone tubular reactor, other reactors can also be used, e.g. Tube reactors with cold gas replenishment, autoclaves or combinations of the different reactor types.
  • Radically decomposing polymerization initiators for the copolymerization according to the present process are preferably tert-butyl peroxypivalate and tert-butyl perisononanoate.
  • any peroxides or peroxide combinations and / or oxygen can also be used as initiators.
  • conventional molecular weight regulators such as propionaldehyde can be used.
  • Suitable inert solvents for the tert-butyl peroxypivalate or the other peroxides are suitably aliphatic hydrocarbons such as octane or mixtures thereof, e.g. Gasoline used. If appropriate, other inert solvents, such as chlorobenzene, cyclohexane or methanol, can also be used.
  • the amounts of solvent required for feeding the initiators are small in relation to the amount of ethylene and are generally 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the amount of ethylene.
  • the solution containing initiators is metered directly into the reaction mixture at the points indicated above, expediently using high-speed metering pumps (cf. EP-A-101 875).
  • ethylene is metered onto the suction side of a high-pressure supercharger together with a mixture consisting of the tertiary amine and an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid or a carboxylic anhydride and / or their derivatives, acrylic acid and methacrylic acid being preferred, in particular acrylic acid.
  • a mixture consisting of the tertiary amine and an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid or a carboxylic anhydride and / or their derivatives acrylic acid and methacrylic acid being preferred, in particular acrylic acid.
  • the copolymerization of the ethylene together with the other carboxylic acid compounds takes place as usual at pressures of 500 to 5000 bar, preferably 1500 to 3000 bar.
  • the temperatures in the polymerization system are between 40 and 350 ° C, preferably between 100 and 350 ° C.
  • the average residence times are usually 30 to 120 seconds.
  • the mean residence time is defined by the ratio of the apparatus volume to the product volume that has passed through the apparatus volume on average per unit of time.
  • the conditions in the polymerization system can be set in terms of equipment most advantageously in so-called tubular reactors.
  • Tubular reactors are tubular polymerization vessels, the length of which is more than 2000 times, preferably 5000 to 50 000 times the tube diameter.
  • Part of the heat of polymerization is preferably removed from the outside with water by cooling the tubular reactor.
  • the polymerization of ethylene or of ethylene with comonomers in the tubular reactor is carried out continuously (cf. "Ullmann's Encyklopadie der Technische Chemie", Verlag Chemie GmbH, D-6940 Weinheim, Volume 19, (1980), pages 169 to 195).
  • Particularly suitable ethylenically unsaturated carboxylic acids and / or their derivatives are compounds such as maleic acid, fumaric acid, itaconic acid, acrylic acid, acrylic acid anhydride, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid hydride.
  • Preferred compounds are methacrylic acid and acrylic acid and especially acrylic acid.
  • the comonomers are polymerized in amounts of from 1 to 30, preferably from 1 to 5,% by weight, based on the ethylene copolymer.
  • Particularly suitable amines are aliphatic tertiary organic amines and preferably trialkylamines having 1 to 18 carbon atoms in the alkyl radical, such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine or dimethyl- (C10 / C18-alkyl) amine Consideration, with tributylamine and dimethyl- (C10 / C18-alkyl) -amine, but especially dimethyl- (C10 / C18-alkyl) -amine, are preferred.
  • Dimethyl- (C10 / C18-alkyl) -amine is understood to mean N, N-dimethyl-N-alkyl-amines, the alkyl radical containing 10 to 18 carbon atoms and usually being a mixture of such alkyl radicals.
  • the amine can be in the preferred range compared to the ethylenically unsaturated carboxylic acid in a slight molar excess, i.e. up to an excess of about 15 mol%, but the amine is preferably in the deficit.
  • the amine-modified ethylene copolymers according to the invention have melt index values of less than 40, preferably 4 to 40 g / 10 min according to DIN 53 735.
  • the densities of the copolymers can be adjusted freely and are preferably between 0.922 and 0.928 g / cm3.
  • amine-modified ethylene copolymers can be prepared in one process step, copolymers having improved homogeneity compared to comparable copolymers being obtained.
  • Films made from the copolymers produced according to the invention have excellent puncture resistance, gloss and transparency and are free of specks.
  • the copolymers can be used to produce adhesion promoters or cable sheathing.
  • the use of ethylene-acrylic acid copolymers for the production of adhesion promoters or cable sheathing is known per se and e.g. in US-A-4 092 488, DE-A-3 607 756, GB-A-2 081 723 and US-A-4 487 885.
  • the copolymerization was carried out in all cases in a tubular reactor with a length / diameter ratio of about 25,000. To remove the heat of polymerization, the tube walls were cooled from the outside with water. The ethylene / amine / carboxylic acid mixture was mixed with the molecular weight regulator propionaldehyde, compressed to the reaction pressure and fed to the inlet point of the reactor. In addition, a solution of tert-butyl peroxypivalate and tert-butyl perisononanoate in diluent (gasoline) was added to the inlet of the reactor.
  • diluent gasoline
  • the molecular weight of the products is adjusted with the molecular weight regulator so that the melt index value is 10 g / 10 min (determined according to DIN 53 735).
  • the resulting copolymer was separated from the unreacted ethylene using the usual separator systems and discharged using a simple KE 150 single-screw extruder from Berstorff.
  • the product is very homogeneous and completely colorless. Films made from this product are speck-free, high-gloss and have excellent puncture resistance.
  • the resulting copolymer was separated from the unreacted ethylene using the usual separator systems and discharged using a simple KE 150 single-screw extruder from Berstorff. Films made from them are very inhomogeneous and contain many specks.
  • the ethylene-acrylic acid copolymer was then reacted with tri-n-butylamine according to the process described in EP-A-193 110 to give the amine-modified ionomer. It still contains many specks and the puncture resistance is lower than that of products obtained according to Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (7)

  1. Procédé de préparation de copolymères d'éthylène de haut poids moléculaire avec des indices de fusion de moins de 40 g/10 mn, par copolymérisation d'éthylène avec des acides carboxyliques ou leurs anhydrides à insaturation α,β-éthylénique et/ou leurs dérivés, dans un système de polymérisation sous des pressions de 500 à 5000 bar et des températures de 40 a 350°C en présence d'amorceurs de polymérisation se décomposant en radicaux libres et éventuellement de régulateurs de poids moléculaire, caractérisé en ce que l'éthylène est également copolymérisé en présence d'une monoamine organique tertiaire.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on effectue la copolymérisation en présence de 10 à environ 100% en moles de l'amine organique tertiaire par rapport au dérivé d'acide carboxylique insaturé mis en réaction.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on effectue la copolymérisation en présence d'amines organiques tertiaires aliphatiques.
  4. Procédé selon la revendication 3, caractérisé en ce qu'on effectue la copolymérisation en présence d'une trialkylamine dont les restes alkyle contiennent de 1 à 18 atomes de carbone.
EP89115873A 1988-09-03 1989-08-29 Procédé de préparation de copolymères amine modifiés de l'éthylène et d'acides carboxyliques, ces copolymères et leur application aux produits adhésifs et aux matériaux d'isolation de cables Expired - Lifetime EP0360038B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89115873T ATE101624T1 (de) 1988-09-03 1989-08-29 Verfahren zur herstellung von aminomodifizierten ethylen-carbonsaeure-copolymerisaten, derartige copolymerisate und ihre verwendung fuer haftvermittler und kabelummantelungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3830007A DE3830007A1 (de) 1988-09-03 1988-09-03 Verfahren zur herstellung von aminmodifizierten ethylen-carbonsaeure-copolymerisaten, derartige copolymerisate und ihre verwendung fuer haftvermittler und kabelummantelungen
DE3830007 1988-09-03

Publications (3)

Publication Number Publication Date
EP0360038A2 EP0360038A2 (fr) 1990-03-28
EP0360038A3 EP0360038A3 (fr) 1992-02-12
EP0360038B1 true EP0360038B1 (fr) 1994-02-16

Family

ID=6362244

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89115873A Expired - Lifetime EP0360038B1 (fr) 1988-09-03 1989-08-29 Procédé de préparation de copolymères amine modifiés de l'éthylène et d'acides carboxyliques, ces copolymères et leur application aux produits adhésifs et aux matériaux d'isolation de cables

Country Status (6)

Country Link
US (2) US4935476A (fr)
EP (1) EP0360038B1 (fr)
JP (1) JPH02107608A (fr)
AT (1) ATE101624T1 (fr)
DE (2) DE3830007A1 (fr)
ES (1) ES2048800T3 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5240544A (en) * 1988-04-05 1993-08-31 Sumitomo Chemical Company, Limited Adhesive composition
GB2228488B (en) * 1989-02-27 1992-03-25 Du Pont Canada Coextrudable adhesives
US5296554A (en) * 1991-10-28 1994-03-22 Showa Denko K.K. Adhesive resin composition
DE4342672A1 (de) * 1993-12-15 1995-06-22 Akzo Nobel Nv Haftverbesserer
US6509007B2 (en) * 2001-03-19 2003-01-21 The Procter & Gamble Company Oral care kits and compositions
US6602966B1 (en) * 2002-07-11 2003-08-05 Equistar Chemicals, Lp In-reactor process for making ethylene polymer nanocomposite materials
US10442952B2 (en) 2015-04-30 2019-10-15 The Chemours Company Fc, Llc Durable architectural coatings containing crosslinkable polymeric additives
KR102251404B1 (ko) 2018-07-03 2021-05-12 주식회사 엘지화학 폴리아릴렌 설파이드의 제조 방법

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US23515A (en) * 1859-04-05 Syrup-charging apparatus
USRE23515E (en) 1949-07-21 1952-06-24 Friction snubber for railway car
GB760178A (en) * 1953-08-19 1956-10-31 Du Pont An improved process for polymerizing ethylene in the presence of polymerization decelerators
US2960496A (en) * 1953-08-19 1960-11-15 Du Pont Process for inhibiting cross-linkages in polyethylene by the use of alkylated hydroxyanisoles or substituted phenyl amines
US3145195A (en) * 1960-05-25 1964-08-18 Borden Co Polyamide resins and process
US3350372A (en) * 1960-08-22 1967-10-31 Gulf Oil Corp Ethylene/acrylate ester copolymers
NL278859A (fr) * 1961-06-21 1900-01-01
US4351931A (en) * 1961-06-26 1982-09-28 E. I. Du Pont De Nemours And Company Polyethylene copolymers
NL129542C (fr) * 1961-08-31 1900-01-01
US3471460A (en) * 1961-08-31 1969-10-07 Du Pont Amine-modified hydrocarbon polymers
NL256395A (fr) * 1962-06-01
US3476722A (en) * 1966-08-15 1969-11-04 Goodrich Co B F Process for polymerizing acrylic acid esters
US3541033A (en) * 1968-03-25 1970-11-17 Union Carbide Corp Crystalline ethylene, alpha-beta olefinically unsaturated carboxylic acid copolymer latex paper coating compositions
US3790521A (en) * 1968-10-07 1974-02-05 Dow Chemical Co Method for making noncolloidal particles like fibers and powders from larger granules of ethylene/carboxylic acid copolymers
US3520861A (en) * 1968-12-26 1970-07-21 Dow Chemical Co Copolymers of ethylene
US3972903A (en) * 1972-12-21 1976-08-03 The Dow Chemical Company Molecular weight control in charge-transfer copolymerization
US4801649A (en) * 1982-12-28 1989-01-31 E. I. Du Pont De Nemours And Company Ionomers having improved low temperature properties and blends thereof with thermoplastic resins
CA1213389A (fr) * 1982-12-28 1986-10-28 Robert J. Statz Ionomeres a tenue amelioree au froid
US4690981A (en) * 1983-03-21 1987-09-01 E. I. Du Pont De Nemours And Company Ionomers having improved low temperature properties

Also Published As

Publication number Publication date
EP0360038A2 (fr) 1990-03-28
ES2048800T3 (es) 1994-04-01
ATE101624T1 (de) 1994-03-15
DE3830007A1 (de) 1990-03-15
US4948850A (en) 1990-08-14
DE58906979D1 (de) 1994-03-24
EP0360038A3 (fr) 1992-02-12
US4935476A (en) 1990-06-19
JPH02107608A (ja) 1990-04-19

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